CN102543237B - Glass solidified body and preparation method thereof - Google Patents
Glass solidified body and preparation method thereof Download PDFInfo
- Publication number
- CN102543237B CN102543237B CN201210039355.2A CN201210039355A CN102543237B CN 102543237 B CN102543237 B CN 102543237B CN 201210039355 A CN201210039355 A CN 201210039355A CN 102543237 B CN102543237 B CN 102543237B
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- glass
- solidified body
- preparation
- glass solidified
- speed
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- 239000011521 glass Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 13
- 230000002285 radioactive effect Effects 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 7
- 230000035882 stress Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 206010042209 Stress Diseases 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 abstract description 19
- 230000008023 solidification Effects 0.000 abstract description 19
- 238000002386 leaching Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002927 high level radioactive waste Substances 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 230000008485 antagonism Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052768 actinide Inorganic materials 0.000 description 4
- 150000001255 actinides Chemical class 0.000 description 4
- 239000002241 glass-ceramic Substances 0.000 description 4
- 241001300078 Vitrea Species 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a glass solidified body and a preparation method thereof, which belong to the field of material preparation of solidified bodies. The glass solidified body comprises components: by mass percentage, 67-74% of Sio2, 13-15% of A12O3, 9-10% of B2O3, and 1-11% of CeO2. The preparation method includes: grinding the components according to proportion and mixing the same uniformly, melting the mixture for 2.5-3.5 hours at the temperature ranging from 1350 DEG C to 1400 DEG C, forming, annealing and cooling finally. The glass solidified body is used for solidification treatment of high-level waste, is fine in chemical stability, evident in solidifying effect and high in leaching rate resistance and has excellent application prospect. The preparation method of the glass solidified body is simple in process, low in melting temperature and easy to control during production.
Description
Technical field
The present invention relates to firming body field of material preparation, be specifically related to a kind of glass solidified body and preparation method thereof.
Background technology
A small amount of actinide in high-level waste can be present in nature for a long time, and causes radiation damage to biosome, and effectively can dispose actinide wherein to the solidification process of high-level waste.The conventional three kinds of methods of solidification process: ceramic solidification, glass ceramics solidification and glass solidification.Ceramic solidification is large to radioelement containing amount in high-level waste, and crystal is strong relative to Vitrea thermal stability, but ceramic solidification is strong to the selectivity of radioelement, and the cold waste material of the major part existed in actual high-level waste produces a very large impact to the effect of ceramic solidification.Glass ceramics solidification just can well solve above ceramic solidification mode Problems existing, radioactive actinide major part is cured in lattice, a large amount of cold refuse and on a small quantity uncured actinide in lattice are then cured in the glass outer matrix that tolerance is large, but this curing mode heat treatment process is comparatively complicated, still be in conceptual phase, practical application is little.Glass solidification is the maximum a kind of curing mode of practical application, a large amount of waste material and nucleic can be comprised in the vitreum of random network structure, cost is lower, technique is comparatively simple, and there is higher corrosion resistance and good waste material subtracts appearance effect, become one comparatively proven technique application in the state such as American-European-Japanese.
Under perfect condition solidification, chemical stability is it is preferred that pure silicon dioxide glass, but its melt temperature is too high, is unfavorable for industrialization.
Summary of the invention
The invention provides a kind of glass solidified body and preparation method thereof, the chemical stability of this firming body is good, and solidification effect is obvious, and during preparation, melt temperature is lower.
A kind of glass solidified body, be calculated in mass percent, its constituent is: SiO
267 ~ 74%, Al
2o
313 ~ 15%, B
2o
39 ~ 10%, radioactive nuclide 1 ~ 11%.
Described radioactive nuclide is preferably CeO
2.
By percentage to the quality, its constituent is preferably:
SiO
267～71.5％，Al
2O
313～14％，B
2O
39～9.5％，CeO
25～11％。In this ratio range, the solidification effect of glass solidified body is better, and after 28 days, the leaching rate of Ce is lower.
Present invention also offers a kind of as described in the preparation method of glass solidified body, comprising:
By the constituent of described glass solidified body ground and mixed in proportion, melting 2.5-3h hour at temperature is 1350-1400 DEG C, then shaping, anneal, cool.
Be warming up to 1350-1400 DEG C with 10 DEG C/min during described melting, be incubated 2.5-3h at this temperature.
The temperature of described annealing is 600-700 DEG C, and the time is 1-2h; Preferably, anneal 2h at temperature is 700 DEG C, eliminates glass internal stress.
Described being molded in the copper-made mould of 300 DEG C of preheatings is carried out, and described cooling is cooled to room temperature with average 2 DEG C/min speed.
SiO
2stability, glass is good, but its melt temperature is too high, is unfavorable for industrialization, and too high levels can reduce crystal production rate in glass ceramic body, reduces the anti-leaching performance of nucleic, therefore, will reach compromise, will add various flux, B on cost and performance
2o
3a kind of well additive, B
2o
3can ensure to maintain Vitrea chemical stability, B when reducing melt temperature in the optional compositional ranges of glass solidified body
2o
3, SiO
2strong Deng the pardon of the borosilicate glass formed to high-level waste kind and quantity, there is excellent forming of glass performance, well chemical stability, structural intergrity and heat and irradiation stability, to the solidification of high-level waste, there is good effect.Al
2o
3glass crystallization tendency can be reduced, ensure chemical stability and the intensity of glass, alleviate the erosion of glass to fire resistive material, but melt temperature can along with Al
2o
3the increase of volume and raising, therefore Al
2o
3volume select 13 ~ 15%, be preferably 13 ~ 14%.
When preparing glass solidified body, under sufficiently high melt temperature, raw material could fully mix, and is conducive to the heat treatment process in later stage.The melt temperature generally preparing glass solidified body is 1500-1600 DEG C, melt temperature is too high, course of reaction is not easy to control, higher to the equipment requirement such as high temperature furnace and fire resistive material, and electric power resource consumption can become the increase of geometric series along with the rising of melt temperature, is unfavorable for cost control and environmental protection.B is added in the present invention
2o
3, B
2o
3be a kind of well additive, the melt temperature of glass solidified body can be reduced to 1400 DEG C, course of reaction is controlled well, the stability maintaining glass solidified body when reducing melt temperature can also be ensured simultaneously, but mix excessive B
2o
3easily make the vitreum after melting produce phase-splitting, work as B
2o
3when content is less than 8%, under equal melt temperature, vitreum can produce macroscopic hole, continues to reduce B
2o
3content greatly can reduce Vitrea melting effect, therefore setting B
2o
3content is 9 ~ 10%, is preferably 9-9.5%.
Glass solidified body of the present invention is for the treatment of the refuse containing high radioactivity nucleic, and solidification effect is obvious, and anti-leaching is effective.
Beneficial effect of the present invention:
Preparation method's technique of the present invention is simple, and melt temperature is low, and production run easily controls, and the glass solidified body chemical stability prepared is good, and solidification effect is obvious, and anti-leaching is effective, for high radioactivity CeO
2time, the glass solidified body of preparation after 28 days its normalized leaching rate, at the 10-6 order of magnitude, has reached the solidification effect of zirconolite glass ceramics firming body 28d, has demonstrated fabulous application prospect.
Embodiment
Embodiment 1
Adopt the pure SiO of dried analysis
274%, Al
2o
315%, B
2o
310%, CeO
21% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning.Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1400 DEG C are warming up to the speed of 10 DEG C/min, insulation 3h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.The glass solidified body obtained is analyzed according to PCT method antagonism leaching performance in ASTM standard, and the normalized leaching rate of the 28d Ce element recorded is 3.6 × 10
-5gm
-2d
-1.
Embodiment 2
Adopt the pure SiO of dried analysis
271.5%, Al
2o
314%, B
2o
39.5%, CeO
25% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning.Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1400 DEG C are warming up to the speed of 10 DEG C/min, insulation 3.5h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.The glass solidified body obtained is analyzed according to PCT method antagonism leaching performance in ASTM standard, and the normalized leaching rate of the 28d Ce element recorded is 6.6 × 10
-6gm
-2d
-1.
Embodiment 3
Adopt the pure SiO of dried analysis
270%, Al
2o
314%, B
2o
39%, CeO
27% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning.Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1350 DEG C are warming up to the speed of 10 DEG C/min, insulation 3h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.The glass solidified body obtained is analyzed according to PCT method antagonism leaching performance in ASTM standard, and the normalized leaching rate of the 28d Ce element recorded is 8.9 × 10
-6gm
-2d
-1.
Embodiment 4
Adopt the pure SiO of dried analysis
267%, Al
2o
313%, B
2o
39%, CeO
211% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning.Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1350 DEG C are warming up to the speed of 10 DEG C/min, insulation 3h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.The glass solidified body obtained is analyzed according to PCT method antagonism leaching performance in ASTM standard, and the normalized leaching rate of the 28d Ce element recorded is 4.1 × 10
-6gm
-2d
-1.
Embodiment 5
By people such as D.M.Wellman at document (D.M.Wellman, J.P.Icenhower, W.J.Weber.Elemental dissolution study of Pu-bearing borosilicate glasses [J] .JNucl Mater, 2005,340:149-162.) disclosed in method adopt the pure SiO of dried analysis
250%, Al
2o
36%, B
2o
37%, CaO 2%, Fe
2o
310%, Li
2o 5%, MgO 1%, MnO
23%, Na
2o9%, NiO 2%, ZrO
24%, PuO in addition
21% does melting at simulated radioactive nuclein 1200 DEG C, 500 DEG C of annealing, and the glass solidified body obtained is analyzed according to ASTM standard antagonism leaching performance, and the normalized leaching rate of the 28d Pu element recorded is only 1.8 × 10
-3gm
-2d
-1.
Claims (2)
1. a preparation method for glass solidified body, is characterized in that, comprising:
Be calculated in mass percent, adopt the pure SiO of dried analysis
270%, Al
2o
314%, B
2o
39%, CeO
27% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning; Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1350 DEG C are warming up to the speed of 10 DEG C/min, insulation 3h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.
2. a preparation method for glass solidified body, is characterized in that, comprising:
Be calculated in mass percent, adopt the pure SiO of dried analysis
271.5%, Al
2o
314%, B
2o
39.5%, CeO
25% does simulated radioactive nuclein, by the accurate raw materials weighing of proportioning; Raw material is after ball mill grinding mixes, pour crucible into, then crucible is inserted elevator furnace, 1400 DEG C are warming up to the speed of 10 DEG C/min, insulation 3.5h, after by the copper-made mould of glass metal down to 300 DEG C of preheatings, then 700 DEG C of annealing 2h eliminate glass internal stresss, are finally cooled to room temperature with the speed of average 2 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210039355.2A CN102543237B (en) | 2012-02-21 | 2012-02-21 | Glass solidified body and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210039355.2A CN102543237B (en) | 2012-02-21 | 2012-02-21 | Glass solidified body and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102543237A CN102543237A (en) | 2012-07-04 |
| CN102543237B true CN102543237B (en) | 2014-12-24 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310781B (en) * | 2014-10-11 | 2017-07-04 | 中国核动力研究设计院 | A kind of glass basis composition and glass solidified body prepared therefrom for middle low-level radioactivity combustible waste burning ash |
| CN104318971B (en) * | 2014-10-11 | 2017-10-03 | 中国核动力研究设计院 | A kind of glass basis composition and glass solidified body prepared therefrom for middle low-level radioactive glass fiber |
| CN104658627B (en) * | 2015-02-02 | 2017-09-01 | 中广核研究院有限公司 | A kind of firming body handled for low and intermediate level radioac glass solidification and method |
| CN110335693A (en) * | 2019-05-27 | 2019-10-15 | 西南科技大学 | A preparation method for radioactive waste vitrified base material and vitrified body |
| CN110335695A (en) * | 2019-05-27 | 2019-10-15 | 西南科技大学 | A kind of radioactive waste solidification base material and preparation method of glass solidification body |
| CN110028248B (en) * | 2019-06-03 | 2020-03-31 | 西南交通大学 | A method for preparing cesium garnet glass-ceramics by low temperature liquid phase sintering |
| CN119612957B (en) * | 2025-01-14 | 2025-09-30 | 清华大学 | A method for preparing a transuranium nuclide glass solidified body |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10167754A (en) * | 1996-12-06 | 1998-06-23 | Toshiba Glass Co Ltd | Vitrifying material for solidifying waste and waste-solidified glass |
| CN101218182A (en) * | 2005-07-15 | 2008-07-09 | 法国原子能委员会 | Method for containing substances by vitrification |
| CN101501786A (en) * | 2006-01-18 | 2009-08-05 | 地理矩阵解决方案公司 | Process and composition for the immobilization of radioactive and hazardous wastes in borosilicate glass |
| CN101826376A (en) * | 2010-05-07 | 2010-09-08 | 西南科技大学 | Preparation method of vitrification substrate for radioactive nuclear waste |
| JP2011011943A (en) * | 2009-07-01 | 2011-01-20 | Denki Kagaku Kogyo Kk | Solidifying agent and solidifying treatment method |
-
2012
- 2012-02-21 CN CN201210039355.2A patent/CN102543237B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10167754A (en) * | 1996-12-06 | 1998-06-23 | Toshiba Glass Co Ltd | Vitrifying material for solidifying waste and waste-solidified glass |
| CN101218182A (en) * | 2005-07-15 | 2008-07-09 | 法国原子能委员会 | Method for containing substances by vitrification |
| CN101501786A (en) * | 2006-01-18 | 2009-08-05 | 地理矩阵解决方案公司 | Process and composition for the immobilization of radioactive and hazardous wastes in borosilicate glass |
| JP2011011943A (en) * | 2009-07-01 | 2011-01-20 | Denki Kagaku Kogyo Kk | Solidifying agent and solidifying treatment method |
| CN101826376A (en) * | 2010-05-07 | 2010-09-08 | 西南科技大学 | Preparation method of vitrification substrate for radioactive nuclear waste |
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| CN102543237A (en) | 2012-07-04 |
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